CN103764700A - Acrylonitrile-acrylate-styrene graft copolymer and thermoplastic resin composition including same - Google Patents
Acrylonitrile-acrylate-styrene graft copolymer and thermoplastic resin composition including same Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
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- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
- C08F291/12—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00 on to nitrogen-containing macromolecules
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- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
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- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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Abstract
The present invention provides an acrylonitrile-acrylate-styrene graft copolymer and a thermoplastic resin composition including same, wherein the copolymer has a structure comprising: a seed consisting of at least one compound of an aromatic vinyl compound, a vinyl cyan compound, and an alkyl(meth)acrylate; a core surrounding the seed and consisting of alkyl acrylate; and a shell surrounding the core and consisting of at least one compound of an aromatic vinyl compound, a vinyl cyan compound, and an alkyl(meth)acrylate, wherein the thickness and the refractive index of each layer are appropriately adjusted.
Description
Technical field
The thermoplastic resin composition who the present invention relates to a kind of acrylonitrile-acrylate-styrene graft copolymer and comprise this multipolymer.More specifically, the present invention relates to a kind ofly there is controlled rubber form and there is the acrylonitrile-acrylate-styrene graft copolymer of refractive index difference in view of the specific refractory power of target matrix polymkeric substance, and the thermoplastic resin composition who comprises the good shock-resistance of having of this multipolymer, weathering resistance and outward appearance.
Background technology
ABS resin is a kind of acrylonitrile-butadiene-styrene terpolymer, because excellent shock-resistance, intensity, chemical resistant properties and processing characteristics are widely used in comprising in the various fields of electrical equipment and electronic product, material of construction and automobile.But ABS resin is owing to being used butadiene polymer as rubber, therefore weathering resistance is poor, is not suitable for outer material.
Meanwhile, in order to obtain the thermoplastic resin with good physicals, weathering resistance and ageing resistance, in acrylonitrile-acrylate-styrene graft copolymer, should not contain ethene unsaturated polymer.Use the ASA (acrylonitrile-styrene-acrylic ester) of crosslink propylene acid alkyl ester rubber polymer to be proved to be the representative instance that is suitable as the thermoplastic resin with excellent weathering resistance and ageing resistance.This ASA resin has good weathering resistance and ageing resistance, and is used in the various application that comprise automobile, boats and ships, leisure goods, material of construction and gardening material.
German Patent No.1,260,135 disclose the method for preparing the ASA polymkeric substance with good weathering resistance and ageing resistance.The core that this method adopts is that average particle diameter is 150 to 800nm and the narrower major diameter cross linked acrylic latex of particle size distribution.The prepared polymer phase ratio with adopting minor diameter polyacrylic ester latex, the polymkeric substance that comprises major diameter polyacrylic ester latex has the notched impact strength of improvement, higher hardness and the shrinking percentage reducing.But compared with minor diameter acrylonitrile-acrylate-styrene graft copolymer, above-mentioned major diameter acrylonitrile-acrylate-styrene graft copolymer has and is difficult to painted shortcoming.
Corresponding ASA polymkeric substance is for the preparation of comparatively limited aspect articles colored.That is to say, can only make light soft color but not strikingly color.
As a reference, at present known material has the tinctorial property of good weathering resistance and mechanical property and improvement.But owing to using with together with the major diameter acrylonitrile-acrylate-styrene graft copolymer of deteriorated tinctorial property, therefore these materials are still not enough to the improvement of tinctorial property.Because these materials'use crosslink propylene acid alkyl ester polymkeric substance are as rubber components, and alkyl acrylate is too low compared to the specific refractory power of vinylbenzene and vinyl cyanide, and therefore these materials cannot obtain color clearly.
In order to overcome above-mentioned shortcoming, the multi-layered acrylic alkyl ester rubber polymer that comprises diene elastomeric polymer is used in the propositions such as Japanese patent publication Sho.47-47863, Japanese patent publication Sho.59-49245, Japanese patent publication Hei.3-66329.
But these patents are adversely not suitable for preparing the resin with good weathering resistance, this is because alkyl acrylate polymeric outer layer does not fully surround diene polymer internal layer.
Summary of the invention
Technical problem
Therefore, an object of the present invention is to provide and a kind ofly there is controlled rubber form and there is the acrylonitrile-acrylate-styrene graft copolymer of refractive index difference in view of the specific refractory power of target matrix polymkeric substance, and the thermoplastic resin composition who comprises the good shock-resistance of having of this multipolymer, weathering resistance and outward appearance.
Technical scheme
According to an aspect of the present invention, above and other object can be by providing a kind of acrylonitrile-acrylate-styrene graft copolymer composition that comprises graft copolymer and matrix polymer to realize, wherein, described graft copolymer comprises: seed, and this seed contains at least one in aromatic vinyl compound, vinyl cyanide compound and (methyl) acrylic acid alkyl ester compound; Rubbery kernel, this rubbery kernel surrounds described seed and contains alkyl acrylate; And shell, this shell surrounds described core and contains at least one in aromatic vinyl compound, vinyl cyanide compound and (methyl) acrylic acid alkyl ester compound; Wherein the form of rubbery kernel meets formula 1 and formula 2 below, the specific refractory power (μ of the specific refractory power of seed or shell and matrix polymer
d 25) difference lower than 0.035, be equal to or less than 0.03 or be equal to or less than 0.02, the specific refractory power (μ of the specific refractory power of core and matrix polymer
d 25) difference higher than 0.056, be equal to or higher than 0.08 or be equal to or higher than 0.1.
Formula 1
140<2*r2<380
Formula 2
r2-r1<80
Wherein, r1 represents the thickness (nm) from the center of graft copolymer to seed, and r2 represents the thickness (nm) from the center of this graft copolymer to core.
Formula 1 can be for example 150≤2*r2≤370,150≤2*r2≤350 or 200≤2*r2≤300.
Formula 2 can be for example 10≤r2-r1≤70,20≤r2-r1≤50 or 20≤r2-r1≤40.
In addition, the acrylonitrile-acrylate-styrene graft copolymer comprising in described acrylonitrile-acrylate-styrene (ASA) graft copolymer composition and the weight ratio of matrix polymer can be 10:90 to 90:10,10:90 to 60:40 or 15:85 to 50:50.
Described matrix polymer can for example be selected from the polymkeric substance that comprises one or more compounds in aromatic vinyl compound, vinyl cyanide compound and (methyl) acrylic acid alkyl ester compound.
According to a further aspect in the invention, provide a kind of moulded product of being prepared by described copolymer compositions, wherein, described moulded product has shock-resistance, weathering resistance, tinctorial property and the gloss of enhancing, thereby has the outward appearance of improvement.
Hereinafter, will describe the present invention in detail.
The invention is characterized in that layer thickness and specific refractory power to seed and core control, thereby a kind of acrylonitrile-acrylate-styrene graft copolymer is provided, and this multipolymer is by controlled rubber form and consider that target matrix refractive index polymer keeps conventional impact property; Based on the specific refractory power of seed being controlled to comparatively similar to the specific refractory power of target matrix polymkeric substance and preventing that tinctorial property is deteriorated; And due to controlling with the refractive index difference of target matrix polymkeric substance the tinctorial property that shows improvement compared with the form of large core, thereby there is good appearance characteristics.
Acrylonitrile-acrylate-styrene graft copolymer according to the present invention can be a kind of ASA graft copolymer, this ASA graft copolymer comprises: seed, and this seed contains at least one in aromatic vinyl compound, vinyl cyanide compound and (methyl) acrylic acid alkyl ester compound; Rubbery kernel, this rubbery kernel surrounds described seed and contains alkyl acrylate; And shell, this shell surrounds described core and contains at least one in aromatic vinyl compound, vinyl cyanide compound and (methyl) acrylic acid alkyl ester compound.
For keeping suitable shock-resistance and improving the consideration of tinctorial property, form the seed of described ASA graft copolymer and the weight ratio of core and shell is particularly preferably (5 to 40): (20 to 60): (20 to 60) or (10 to 35): (30 to 55): (30 to 50).
In addition, when the consumption of core is during lower than the above scope limiting, the content of rubber is lower, and the shock-resistance of graft copolymer strengthens therefore deteriorated; And when the content of rubber exceedes the scope of above restriction and the content of shell lower than this scope, rubber particles may lump in accumulation process, the effect that strengthens shock-resistance reduces, and resin compatible is quite low, and cannot obtain required index level.
When the content of seed is lower, appearance characteristics is poor; And when the too high levels of seed, shock strength is deteriorated.
In addition, when the content of alkyl acrylate of composition core is lower, the content of rubber is lower, and shock-resistance is therefore deteriorated; And when the too high levels of alkyl acrylate, rubber particles may lump compared with low due to the content of described shell, resin compatible is quite low, and the effect that strengthens shock-resistance reduces, and specific refractory power also reduces.
The example of the alkyl acrylate containing in core comprises: methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, Ethyl acrylate, Octyl acrylate and 2-EHA etc.Particularly, described alkyl acrylate can be n-butyl acrylate or 2-EHA etc.
Described rubbery kernel can be the acrylic rubber that material by making to comprise alkyl acrylate and linking agent polymerization make.When containing linking agent, can control gel content, and intensity is comparatively excellent.
Meanwhile, with regard to keeping the balance between shock-resistance and tinctorial property, the average particle diameter from seed to core higher than 0.14 μ m and lower than 0.38 μ m, is preferably 0.15 to 0.37 μ m, 0.15 to 0.35 μ m or 0.2 to 0.3 μ m for for example.
The aromatic vinyl compound that can be used for seed and shell herein, can comprise be selected from vinylbenzene, α-vinylbenzene, at least one in vinylbenzene, Vinyl toluene and styrene monomer derivative.
In addition, can be used for the vinyl cyanide compound of seed and shell can be for vinyl cyanide, methacrylonitrile or its mixture.
(methyl) acrylic acid alkyl ester compound that can be used for seed and shell can comprise at least one being selected from methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, 2-EHA, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, 2-Ethylhexyl Methacrylate, ethylacrylic acid methyl esters and ethyl propylene acetoacetic ester.
In one embodiment, seed and/or core can also comprise at least one by general formula 1 represents below compound as linking agent:
General formula 1
Wherein, A represents the substituting group that contains vinyl or (methyl) acrylate group independently, and A' represents hydrogen base, the substituting group that contains vinyl, the alkyl of C1 to C30, the aralkyl of C5 to C24, the virtue amino of C5 to C24 or the aryl of C6 to C30,
R represents divalence ethyl or propyl group independently, and n is 0 to 15,0 to 5 or 0 to 4 integer.
In another embodiment, described seed and/or described core can also comprise be selected from following compound at least one as linking agent: Vinylstyrene, 1, 3-butylene glycol diacrylate, 1, 3-butylene glycol dimethacrylate, 1, 4-butylene glycol diacrylate, 1, 4-butylene glycol dimethacrylate, vinylformic acid aryl ester, aryl methacrylate, Viscoat 295, Viscoat 335HP, ethylene glycol dimethacrylate, Diethylene Glycol dimethacrylate, triethylene glycol dimethacrylate, neopentylglycol dimethacrylate, triallyl isocyanurate, triarylamine and diallyl amine.
Based on the monomer for the preparation of described ASA quasi-graft copolymer that amounts to 100 weight parts, the consumption of described linking agent is for example 0.01 to 5 weight part or 0.1 to 3 weight part.
In addition, the monomer of the described ASA quasi-graft copolymer of composition based on total 100 weight parts, the content of described shell is for example 20 to 60 weight parts.When the content of shell is lower, grafting efficiency is deteriorated, and rubber lumps, and resin compatible declines, and the reinforced effects of shock-resistance is deteriorated; And when the too high levels of shell, shock-resistant usefulness is adversely deteriorated because the relative content of rubber reduces.
In one embodiment, for polymerisation reactivity and specific refractory power are controlled to desired level, described shell is to comprise at least one the multipolymer being selected from alkyl methacrylate, aromatic vinyl compound and vinyl cyanide compound, and forms by graft polymerization.
In another embodiment, described shell is the multipolymer that comprises aromatic vinyl compound and vinyl cyanide compound or comprise aromatic vinyl compound, vinyl cyanide compound and alkyl methacrylate, and forms by graft polymerization.
The final gel content of described ASA graft copolymer lower than 92%, or lower than 90%, or is 30 to 90% for for example; And its graft ratio is higher than 20%, is equal to or higher than 25%, or be 25 to 100% or 25 to 80%.When gel content falls in the scope of above restriction, intensity is comparatively excellent; When graft ratio is in the above scope limiting, due to the improvement of the situation of gathering comparatively favourable aspect dispersion.
The form of described rubbery kernel meets formula 1 and formula 2 below:
Formula 1
150≤2*r2≤350
Formula 2
20≤r2-r1≤50
Wherein, r1 represents the thickness (nm) from the center of graft copolymer to seed, and r2 represents the thickness (nm) from the center of graft copolymer to core.
R1 is for example radius or the mean radius of seed, 1/2 of the particle dia of seed or average particle diameter.
R2 is for example radius or the mean radius that comprises the core of seed, comprises 1/2 of the particle dia of core of seed or average particle diameter.
By following example, can be confirmed, when meeting the above-mentioned formula relevant with the thickness of seed and core, with the thickness reduction of the larger core part of matrix part refractive index difference, and the size of core obtained suitable control, thereby the transparency is provided and significantly strengthened the effect of tinctorial property.
In addition, the invention is characterized in the specific refractory power (μ of the specific refractory power of seed and/or shell and matrix polymer
d 25) difference lower than 0.035, and the specific refractory power (μ of the specific refractory power of core and matrix polymer
d 25) difference higher than 0.056.Described matrix polymer can be at least one being selected from one or more the matrix polymer comprising in aromatic vinyl compound, vinyl cyanide compound and (methyl) acrylic acid alkyl ester compound.
Described matrix polymer can be for example hard matrix resin.
Described hard matrix resin refers to that second-order transition temperature is at least 80 ℃ or is the resin that comprises the monomer that forms hard polymer of 80 to 200 ℃.
As another example, described hard matrix resin can be SAN (styrene-acrylonitrile) resin.
With regard to give described graft copolymer tinctorial property on transparent basis with regard to, the specific refractory power (μ of the specific refractory power of seed or the specific refractory power of shell and matrix polymer
d 25) difference preferably lower than 0.035, be equal to or less than 0.03 or lower than 0.03.
With regard to the remarkable improvement in tinctorial property, the specific refractory power (μ of the specific refractory power of core and matrix polymer
d 25) difference be higher than 0.056, or be equal to or higher than 0.08, or be 0.06 to 0.15 or 0.08 to 0.13.When use the relatively high divinyl of specific refractory power, vinylbenzene etc. as core when reducing the difference in specific refractory power, weathering resistance and shock strength all adversely occur deteriorated.
Particularly, according to ASA graft copolymer composition of the present invention, can comprise aforesaid propylene nitrile-Acrylate-styrene bipolymer graft copolymer and at least one the hard matrix resin in aromatic vinyl compound, vinyl cyanide compound and (methyl) acrylic acid alkyl ester compound that contains as thermoplastic matrix resin using the weight ratio of 10:90 to 90:10.
Described acrylonitrile-acrylate-styrene graft copolymer can adopt method well known in the art, and for example prepared by emulsion polymerization.
In another example, acrylonitrile-acrylate-styrene graft copolymer of the present invention can be prepared by three steps below.As a reference, the content of described acrylonitrile-acrylate-styrene graft copolymer is take the monomer for the preparation of this acrylonitrile-styrene-acrylic ester copolymer that amounts to 100 weight parts as benchmark.
First, in first step, by least one monomer or the monomer mixture polymerization that makes to be selected from comprising of 4 to 30 weight parts in aromatic vinyl compound, vinyl cyanide compound and (methyl) acrylic acid alkyl ester compound, prepare seed.Described monomer mixture can also for example comprise the ionogen of 0.001 to 1 weight part, linking agent, the polymerization starter of 0.01 to 3 weight part and the emulsifying agent of 0.01 to 5 weight part of 0.01 to 3 weight part.
Then, in second step, under the existence of above-mentioned seed, core is prepared in the monomer mixture polymerization of the linking agent by the alkyl acrylate monomer that makes to comprise 20 to 80 weight parts and 0.01 to 3 weight part.In addition, described monomer mixture can also comprise the polymerization starter of 0.01 to 3 weight part and the emulsifying agent of 0.01 to 5 weight part.
Then, in third step, under the existence of above-mentioned rubbery kernel, by least one monomer or the monomer mixture polymerization being selected from aromatic vinyl compound, vinyl cyanide compound and (methyl) alkyl acrylate that makes 10 to 70 weight parts, prepare graft shell.In addition, described monomer mixture can also for example comprise polymerization starter, the molecular weight regulator of 0 to 3 weight part and the emulsifying agent of 0.01 to 5 weight part of 0.01 to 3 weight part.
Based on the ASA graft copolymer and the matrix resin that amount to 100 weight parts, thermoplastic resin composition of the present invention can also comprise at least one additive in fire retardant, lubricant, antiseptic-germicide, releasing agent, nucleator, softening agent, thermo-stabilizer, antioxidant, photostabilizer, ultra-violet stabilizer, expanding material, pigment, dyestuff and inorganic additives that is selected from of 0.1 to 10 weight part.
In another example, based on the ASA graft copolymer and the matrix resin that amount to 100 weight parts, described thermoplastic resin composition can also comprise at least one additive in lubricant, antioxidant, ultra-violet stabilizer, pigment and inorganic additives that is selected from of 0.1 to 5 weight part or 0.1 to 3 weight part.
The moulded product of being prepared by thermoplastic resin composition of the present invention shows shock-resistance, weathering resistance, tinctorial property and the gloss of improvement, thereby there is the outward appearance of enhancing, thereby can be used for auto parts machinery, electrical equipment and electronic component or material of construction, but the present invention is not limited to these application.
Beneficial effect
Advantageously, the invention provides a kind of acrylonitrile-acrylate-styrene graft copolymer, this multipolymer is in view of the specific refractory power of target matrix polymkeric substance and keep conventional impact property; Owing to the specific refractory power of seed being controlled to and comparatively similar the deteriorated of tinctorial property that prevent of specific refractory power of target matrix polymkeric substance; And due to controlling with the form of the larger core of the refractive index difference of target matrix polymkeric substance, when being applied to thermoplastic resin composition, demonstrated good outward appearance.
Embodiment
Now, will provide preferred embodiment for understanding better the present invention.Provide these embodiment only for illustrating the present invention, and should not be construed as the restriction to scope and spirit of the present invention.
embodiment 1
By mixing the acrylonitrile-acrylate-styrene graft copolymer of 40 weight parts, styrene-acrylonitrile copolymer (the AN of the SM that contains 45 weight parts and 15 weight parts of 60 weight parts, and specific refractory power is 1.573), the lubricant of 1 weight part, the ultra-violet stabilizer of the antioxidant of 0.5 weight part and 0.5 weight part, preparation thermoplastic resin composition, the vinylbenzene that described acrylonitrile-acrylate-styrene graft copolymer comprises 20 % by weight is as seed, the butyl acrylate of 45 % by weight is as core, and the styrene-acrylonitrile of 35 % by weight (AN of the SM that contains 26.25 % by weight and 8.75 % by weight) is as shell, and r1 is 75nm, r2 is 115nm.In this case, the specific refractivity of the seed of acrylonitrile-acrylate-styrene graft copolymer or shell and matrix is lower than 0.02, the specific refractivity of core and matrix is 0.11, and the gel content of this acrylonitrile-acrylate-styrene graft copolymer is lower than 90%, and graft ratio is 35%.
As a reference, can obtain required r1 and r2 level by control the content of emulsifying agent in polymerization process, and SM refers to styrene monomer, AN refers to acrylonitrile monemer, MMA refers to methyl methacrylate, and BA refers to butyl acrylate, and 2-EHA refers to 2-EHA.
embodiment 2
To prepare thermoplastic resin composition with the same way described in embodiment 1, difference is: use the vinylbenzene of 10 % by weight as seed, use the butyl acrylate of 55 % by weight as core, use the styrene-acrylonitrile (AN of the SM that contains 26.25 % by weight and 8.75 % by weight) of 35 % by weight as shell, r1 is 35nm, and r2 is 75nm.In this case, specific refractivity, gel content and graft ratio are with identical described in embodiment 1.
embodiment 3
To prepare thermoplastic resin composition with the same way described in embodiment 1, difference is: use the vinylbenzene of 25 % by weight as seed, use the butyl acrylate of 45 % by weight as core, use the styrene-acrylonitrile (AN of the SM that contains 22.5 % by weight and 7.5 % by weight) of 30 % by weight as shell, r1 is 110nm, r2 is 150nm, and graft ratio is 28%.In this case, specific refractivity and gel content are with identical described in embodiment 1.
embodiment 4
To prepare thermoplastic resin composition with the same way described in embodiment 1, difference is: use the vinylbenzene of 30 % by weight as seed, use the butyl acrylate of 40 % by weight as core, use the styrene-acrylonitrile (AN of the SM that contains 22.5 % by weight and 7.5 % by weight) of 30 % by weight as shell, r1 is 135nm, r2 is 175nm, and graft ratio is 25%.In this case, specific refractivity and gel content are with identical described in embodiment 1.
embodiment 5
To prepare thermoplastic resin composition with the same way described in embodiment 1, difference is: use the vinylbenzene of 25 % by weight as seed, use the butyl acrylate of 45 % by weight as core, use the styrene-acrylonitrile (AN of the SM that contains 22.5 % by weight and 7.5 % by weight) of 30 % by weight as shell, r1 is 80nm, r2 is 110nm, and graft ratio is 28%, and gel content is 90%.In this case, specific refractivity is with identical described in embodiment 1.
embodiment 6
To prepare thermoplastic resin composition with the same way described in embodiment 1, difference is: use the vinylbenzene of 25 % by weight as seed, use the butyl acrylate of 35 % by weight as core, use the styrene-acrylonitrile (AN of the SM that contains 30 % by weight and 10 % by weight) of 40 % by weight as shell, r1 is 100nm, r2 is 130nm, and graft ratio is 40%, and gel content is 85%.In this case, specific refractivity is with identical described in embodiment 1.
embodiment 7
To prepare thermoplastic resin composition with the same way described in embodiment 1, difference is: use the vinylbenzene of 15 % by weight as seed, use the butyl acrylate of 45 % by weight as core, use the styrene-acrylonitrile (AN of the SM that contains 30 % by weight and 10 % by weight) of 40 % by weight as shell, r1 is 70nm, r2 is 120nm, and graft ratio is 45%.In this case, specific refractivity and gel content are with identical described in embodiment 1.
embodiment 8
To prepare thermoplastic resin composition with the same way described in embodiment 1, difference is: use the vinylbenzene of 20 % by weight as seed, use the butyl acrylate of 45 % by weight as core, use the styrene-acrylonitrile (AN of the SM that contains 26.25 % by weight and 8.75 % by weight) of 35 % by weight as shell, r1 is 100nm, and r2 is 150nm.In this case, specific refractivity, gel content and graft ratio are with identical described in embodiment 1.
embodiment 9
To prepare thermoplastic resin composition with the same way described in embodiment 1, difference is: use the vinylbenzene of 25 % by weight as seed, use the butyl acrylate of 30 % by weight as core, use the styrene-acrylonitrile (AN of the SM that contains 33.75 % by weight and 11.25 % by weight) of 45 % by weight as shell, r1 is 90nm, r2 is 110nm, and graft ratio is 45%, and gel content is 80%.In this case, specific refractivity is with identical described in embodiment 1.
embodiment 10
To prepare thermoplastic resin composition with the same way described in embodiment 1, difference is: use the vinylbenzene of 35 % by weight as seed, use the butyl acrylate of 30 % by weight as core, use the styrene-acrylonitrile (AN of the SM that contains 26.25 % by weight and 8.75 % by weight) of 35 % by weight as shell, r1 is 115nm, and r2 is 135nm.In this case, specific refractivity, gel content and graft ratio are with identical described in embodiment 1.
embodiment 11
To prepare thermoplastic resin composition with the same way described in embodiment 1, difference is: use styrene-acrylonitrile-methyl methacrylate (MMA of the SM that contains 15 % by weight, the AN of 2 % by weight and 3 % by weight) as seed, and the seed of acrylonitrile-acrylate-styrene graft copolymer and the specific refractivity of matrix are lower than 0.03.In this case, gel content and graft ratio are with identical described in embodiment 1.
embodiment 12
To prepare thermoplastic resin composition with the same way described in embodiment 1, difference is: use Styrene And Butyl-acrylate (BA of the SM that contains 15 % by weight and 5 % by weight) as seed, and the seed of acrylonitrile-acrylate-styrene graft copolymer and the specific refractivity of matrix are lower than 0.03.In this case, gel content and graft ratio are with identical described in embodiment 1.
embodiment 13
To prepare thermoplastic resin composition with the same way described in embodiment 1, difference is: use styrene-acrylonitrile (AN of the SM that contains 15 % by weight and 5 % by weight) as seed, and the seed of acrylonitrile-acrylate-styrene graft copolymer and the specific refractivity of matrix are lower than 0.02.In this case, gel content and graft ratio are with identical described in embodiment 1.
embodiment 14
To prepare thermoplastic resin composition with the same way described in embodiment 1, difference is: use styrene-acrylonitrile-butyl acrylate (AN of the SM that contains 12 % by weight, the BA of 4 % by weight and 4 % by weight) as seed, and the seed of acrylonitrile-acrylate-styrene graft copolymer and the specific refractivity of matrix are lower than 0.03.In this case, gel content and graft ratio are with identical described in embodiment 1.
embodiment 15
To prepare thermoplastic resin composition with the same way described in embodiment 1, difference is: use butyl acrylate-2-EHA (2-EHA of the BA that contains 25 % by weight and 20 % by weight) as core, and the core of acrylonitrile-acrylate-styrene graft copolymer and the specific refractivity of matrix are 0.115.In this case, gel content and graft ratio are with identical described in embodiment 1.
embodiment 16
To prepare thermoplastic resin composition with the same way described in embodiment 1, difference is: use styrene-acrylonitrile-methyl methacrylate (MMA of the SM that contains 26.25 % by weight, the AN of 3.5 % by weight and 5.25 % by weight) as shell, and the shell of acrylonitrile-acrylate-styrene graft copolymer and the specific refractivity of matrix are lower than 0.03.In this case, gel content and graft ratio are with identical described in embodiment 1.
comparative example 1
To prepare thermoplastic resin composition with the same way described in embodiment 1, difference is: use the vinylbenzene of 4 % by weight as seed, use the butyl acrylate of 55 % by weight as core, use the styrene-acrylonitrile (AN of the SM that contains 30.75 % by weight and 10.25 % by weight) of 41 % by weight as shell, r1 is 55nm, r2 is 135nm, and graft ratio is 45%.In this case, specific refractivity and gel content are with identical described in embodiment 1.
comparative example 2
To prepare thermoplastic resin composition with the same way described in embodiment 1, difference is: use the vinylbenzene of 30 % by weight as seed, use the butyl acrylate of 40 % by weight as core, use the styrene-acrylonitrile (AN of the SM that contains 22.5 % by weight and 7.5 % by weight) of 30 % by weight as shell, r1 is 50nm, r2 is 70nm, and graft ratio is 28%.In this case, specific refractivity and gel content are with identical described in embodiment 1.
comparative example 3
To prepare thermoplastic resin composition with the same way described in embodiment 1, difference is: use the vinylbenzene of 30 % by weight as seed, use the butyl acrylate of 40 % by weight as core, use the styrene-acrylonitrile (AN of the SM that contains 22.5 % by weight and 7.5 % by weight) of 30 % by weight as shell, r1 is 140nm, r2 is 190nm, and graft ratio is 28%.In this case, specific refractivity and gel content are with identical described in embodiment 1.
comparative example 4
To prepare thermoplastic resin composition with the same way described in embodiment 1, difference is: use the vinylbenzene of 10 % by weight as seed, use the butyl acrylate of 55 % by weight as core, use the styrene-acrylonitrile (AN of the SM that contains 26.25 % by weight and 8.75 % by weight) of 35 % by weight as shell, r1 is 100nm, r2 is 190nm, and graft ratio is 35%.In this case, specific refractivity and gel content are with identical described in embodiment 1.
comparative example 5
To prepare thermoplastic resin composition with the same way described in embodiment 1, difference is: use the vinylbenzene of 10 % by weight as seed, use the butyl acrylate of 50 % by weight as core, use the styrene-acrylonitrile (AN of the SM that contains 30 % by weight and 10 % by weight) of 40 % by weight as shell, r1 is 75nm, r2 is 115nm, and the specific refractivity of described seed and matrix is higher than 0.035, and graft ratio is 40%.In this case, specific refractivity and gel content are with identical described in embodiment 1.
comparative example 6
To prepare thermoplastic resin composition with the same way described in embodiment 1, difference is: use styrene-acrylonitrile-methyl methacrylate (MMA of the SM that contains 7 % by weight, the AN of 3 % by weight and 10 % by weight) as seed, and the seed of acrylonitrile-acrylate-styrene graft copolymer and the specific refractivity of matrix are 0.04.In this case, gel content and graft ratio are with identical described in embodiment 1.
comparative example 7
To prepare thermoplastic resin composition with the same way described in embodiment 1, difference is: use Styrene And Butyl-acrylate (BA of the SM that contains 9 % by weight and 11 % by weight) as seed, and the seed of acrylonitrile-acrylate-styrene graft copolymer and the specific refractivity of matrix are 0.05.In this case, gel content and graft ratio are with identical described in embodiment 1.
comparative example 8
To prepare thermoplastic resin composition with the same way described in embodiment 1, difference is: use styrene-acrylonitrile-butyl acrylate (BA of the SM that contains 8 % by weight, the AN of 4 % by weight and 8 % by weight) as seed, and the seed of acrylonitrile-acrylate-styrene graft copolymer and the specific refractivity of matrix are 0.05.In this case, gel content and graft ratio are with identical described in embodiment 1.
comparative example 9
To prepare thermoplastic resin composition with the same way described in embodiment 1, difference is: use BA-St (BA of the SM that contains 9 % by weight and 11 % by weight) as core, and the core of acrylonitrile-acrylate-styrene graft copolymer and the specific refractivity of matrix are 0.05.In this case, gel content and graft ratio are with identical described in embodiment 1.
comparative example 10
To prepare thermoplastic resin composition with the same way described in embodiment 1, difference is: use butyl divinyl as core, and the core of acrylonitrile-acrylate-styrene graft copolymer and the specific refractivity of matrix are 0.056.In this case, gel content and graft ratio are respectively 94% and 45%.
[test example]
By the character of method assessment ASA graft copolymer composition below.
(1) specific refractory power: powder is compressed, and use refractometer (Metricon2010) to measure its specific refractory power.
(2) average particle diameter of seed/core/shell: the average particle diameter of each latex adopts dynamic laser light scattering method, is used NICOMP380 particle size analyzer.Under Gaussian measurement pattern, intensity is measured.In addition, for prepared acrylonitrile-acrylate-styrene graft copolymer, use TEM (Jeol.JEM-1400) to measure maximum seed, core and the shell diameter corresponding to 10% particle of particle dia maximum with the acceleration voltage of 120KV and 1 spot size ratio (× 10K, × 25K, × 50K), and calculate its mean value.
As a reference, r1 is by the average particle diameter of seed is calculated divided by 2, and r2 is by calculating the average particle diameter of the core that comprises this seed divided by 2.
(3) cantilever beam type shock strength (1/4' otch at 23 ℃, kgfcm/cm): measure according to ASTM D-256 method.
(4) coloring resin performance: in plastic resin treatment process, add the carbon black of 1wt%, and use color difference meter to measure the L value of the sample for measuring tinctorial property.When L value reduces, color reaches aterrimus, represents that the tinctorial property of pigment improves.
(5) gloss (45 °): measure according to ASTM D528.
(6) weathering resistance: according to ASTM G155-1, use weatherometer that sample is kept 2,000 hours, then use color difference meter to measure colour-change (Δ E).Δ E represents the arithmetical av of the forward and backward CIE Lab value of atmospheric exposure test.When Δ E levels off to zero (0) time, weathering resistance improves.
(7) gel content and graft ratio: add acetone in 1g ASA graft copolymer powder, then at room temperature stir 24 hours and centrifugal.Only be collected in the component that there is no dissolving in acetone, and measure the weight in dry front and rear.Gel content is tried to achieve by formula below.
* gel content (%)=(in the centrifugal and dry weight of the weight/sample of sample afterwards) × 100
* graft ratio (%)=(weight of the weight/nuclear polymer of grafted monomer) × 100
Take the rubber form of formula 1 and formula 2 and refractive index difference, (specific refractivity of seed or shell and matrix resin is as 0.03 or be less than 0.03, the specific refractivity of core and matrix resin is 0.08 or is greater than 0.08) etc. for benchmark, the physical property measurement relevant with comparative example 1 to 10 with embodiment 1 to 16 be the results are summarized in following table 1 to 3.
[table 1]
| Classification | Comparative example 1 to 5 | Comparative example 6 to 8 | Comparative example 9 and 10 |
| The specific refractory power of seed | ? | Improper | ? |
| The specific refractory power of core | ? | ? | Improper |
| The thickness of core and size | Improper | ? | ? |
[table 2]
| Classification | Shock strength | Weathering resistance | Gloss | Tinctorial property |
| Embodiment 1 | 19 | 1.6 | 95 | 27.0 |
| Embodiment 2 | 16 | 1.4 | 98 | 26.5 |
| Embodiment 3 | 23 | 1.9 | 92 | 27.2 |
| Embodiment 4 | 25 | 2.0 | 91 | 27.5 |
| Embodiment 5 | 18 | 1.5 | 95 | 26.8 |
| Embodiment 6 | 29 | 1.5 | 95 | 26.9 |
| Embodiment 7 | 18 | 1.7 | 99 | 27.3 |
| Embodiment 8 | 24 | 1.8 | 93 | 27.4 |
| Embodiment 9 | 17 | 1.4 | 98 | 26.3 |
| Embodiment 10 | 18 | 1.5 | 96 | 26.5 |
| Embodiment 11 | 18 | 1.5 | 98 | 26.7 |
| Embodiment 12 | 19 | 1.4 | 95 | 26.9 |
| Embodiment 13 | 19 | 1.4 | 96 | 26.8 |
| Embodiment 14 | 18 | 1.6 | 97 | 26.7 |
| Embodiment 15 | 21 | 1.6 | 94 | 27.3 |
| Embodiment 16 | 18 | 1.2 | 96 | 26.5 |
[table 3]
| Classification | Shock strength | Weathering resistance | Gloss | Tinctorial property |
| Comparative example 1 | 22 | 2.0 | 85 | 29.0 |
| Comparative example 2 | 6 | 1.5 | 95 | 26.5 |
| Comparative example 3 | 25 | 1.7 | 81 | 29.3 |
| Comparative example 4 | 25 | 1.6 | 88 | 29.8 |
| Comparative example 5 | 21 | 1.5 | 75 | 30.6 |
| Comparative example 6 | 16 | 1.4 | 95 | 29.2 |
| Comparative example 7 | 20 | 1.5 | 91 | 29.5 |
| Comparative example 8 | 19 | 1.5 | 93 | 29.4 |
| Comparative example 9 | 7 | 1.6 | 95 | 26.5 |
| Comparative example 10 | 25 | 8.6 | 98 | 26.5 |
From upper table 2, compared with comparative example 1 to 10, embodiment 1 to 16 has similar or good shock strength, excellent tinctorial property and gloss, good outward appearance and weathering resistance, and in physicals good population equilibrium.
Meanwhile, from upper table 3, the thickness of core and off size suitable comparative example 1 to 5 have shown that tinctorial property is deteriorated higher than upper when thickness or size in limited time, and have shown that shock strength is greatly deteriorated lower than lower when thickness or size in limited time.Comparative example 6 to 10 shown specific refractory power when seed and matrix when improper tinctorial property deteriorated, and it is deteriorated to have shown when using divinyl that specific refractory power is higher or vinylbenzene as core weathering resistance and shock strength.
Claims (15)
1. an ASA graft copolymer composition, comprises:
ASA graft copolymer, this multipolymer comprises seed, core and shell; And
Matrix polymer,
Wherein, the specific refractory power (μ of the specific refractory power of described seed and described matrix polymer
d 25) difference lower than 0.035,
Specific refractory power (the μ of the specific refractory power of described shell and described matrix polymer
d 25) difference lower than 0.035,
Specific refractory power (the μ of the specific refractory power of described core and described matrix polymer
d 25) difference higher than 0.056, and
Described ASA graft copolymer meets formula 1 and formula 2 below:
Formula 1
140<2*r2<380
Formula 2
r2-r1<80
Wherein, r1 represents the thickness (nm) from the center of graft copolymer to seed, and r2 represents the thickness (nm) from the center of graft copolymer to core.
2. ASA graft copolymer composition according to claim 1, wherein, the gel content of described ASA graft copolymer is lower than 92%.
3. ASA graft copolymer composition according to claim 1, wherein, the graft ratio of described ASA graft copolymer is higher than 20%.
4. ASA graft copolymer composition according to claim 1, wherein, described ASA graft copolymer comprises:
Seed, this seed contains at least one compound in aromatic vinyl compound, vinyl cyanide compound and (methyl) acrylic acid alkyl ester compound;
Rubbery kernel, this rubbery kernel surrounds described seed and contains alkyl acrylate; And
Shell, this shell surrounds described core and contains at least one compound in aromatic vinyl compound, vinyl cyanide compound and (methyl) acrylic acid alkyl ester compound.
5. ASA graft copolymer composition according to claim 1, wherein, the weight ratio of described seed and described core and described shell is 5 to 40:20 to 60:20 to 60.
6. ASA graft copolymer composition according to claim 4, wherein, described alkyl acrylate comprises at least one being selected from methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, Ethyl acrylate, Octyl acrylate and 2-EHA.
7. ASA graft copolymer composition according to claim 4, wherein, described aromatic vinyl compound comprise be selected from vinylbenzene, α-vinylbenzene, at least one in vinylbenzene, Vinyl toluene and styrene monomer derivative.
8. ASA graft copolymer composition according to claim 4, wherein, described vinyl cyanide compound comprises vinyl cyanide, methacrylonitrile or its mixture.
9. ASA graft copolymer composition according to claim 4, wherein, described (methyl) acrylic acid alkyl ester compound comprises at least one being selected from methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, 2-EHA, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, 2-Ethylhexyl Methacrylate, ethylacrylic acid methyl esters and ethyl propylene acetoacetic ester.
10. ASA graft copolymer composition according to claim 1, wherein, described seed and/or described core comprise be selected from following compound at least one as linking agent: Vinylstyrene, 1, 3-butylene glycol diacrylate, 1, 3-butylene glycol dimethacrylate, 1, 4-butylene glycol diacrylate, 1, 4-butylene glycol dimethacrylate, vinylformic acid aryl ester, aryl methacrylate, Viscoat 295, Viscoat 335HP, ethylene glycol dimethacrylate, Diethylene Glycol dimethacrylate, triethylene glycol dimethacrylate, neopentylglycol dimethacrylate, triallyl isocyanurate, triarylamine, diallyl amine and by general formula 1 represents below compound:
General formula 1
In general formula 1, A represents the substituting group that contains vinyl or (methyl) acrylate group independently, A' represents hydrogen base, the substituting group that contains vinyl, the alkyl of C1 to C30, the aralkyl of C5 to C24, the virtue amino of C5 to C24 or the aryl of C6 to C30
R represents ethyl or propyl group independently, and n is 0 to 15 integer.
11. ASA graft copolymer compositions according to claim 10, wherein, based on the monomer for the preparation of described ASA graft copolymer that amounts to 100 weight parts, the consumption of described linking agent is 0.01 to 5 weight part.
12. ASA graft copolymer compositions according to claim 1, wherein, described matrix polymer comprises at least one being selected from hard matrix polymer, and this hard matrix polymer contains one or more in aromatic vinyl compound, vinyl cyanide compound and (methyl) acrylic acid alkyl ester compound.
13. ASA graft copolymer compositions according to claim 1, wherein, described ASA graft copolymer and described matrix polymer exist with the weight ratio of 10:90 to 90:10.
14. ASA graft copolymer compositions according to claim 1, wherein, based on the described ASA graft copolymer composition that amounts to 100 weight parts, at least one additive in fire retardant, lubricant, antiseptic-germicide, releasing agent, nucleator, softening agent, thermo-stabilizer, antioxidant, photostabilizer, expanding material, pigment, dyestuff and inorganic additives that is selected from that this ASA graft copolymer composition comprises 0.1 to 10 weight part.
15. 1 kinds of moulded products, it is by preparing according to the ASA graft copolymer composition described in any one in claim 1 to 14.
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| KR1020130082681A KR101425754B1 (en) | 2012-08-27 | 2013-07-15 | Graft copolymer and thermoplastic resin composition comprising thereof |
| PCT/KR2013/006356 WO2014035055A1 (en) | 2012-08-27 | 2013-07-16 | Acrylonitrile-acrylate-styrene graft copolymer and thermoplastic resin composition including same |
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| EP (1) | EP2889317B1 (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP2889317B1 (en) | 2016-12-07 |
| JP2014527570A (en) | 2014-10-16 |
| EP2889317A4 (en) | 2016-03-30 |
| JP5948716B2 (en) | 2016-07-06 |
| EP2889317A1 (en) | 2015-07-01 |
| CN103764700B (en) | 2016-09-21 |
| WO2014035055A1 (en) | 2014-03-06 |
| KR20140027872A (en) | 2014-03-07 |
| US20140235749A1 (en) | 2014-08-21 |
| US9353255B2 (en) | 2016-05-31 |
| KR101425754B1 (en) | 2014-08-05 |
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